Process for improving the waste gas fastness of dyed cellulose derivatives



"ilited States Patent PRGCESS FOR IMPRQVING THE WASTE GAS FASTNESS F DYED CEiLLULOSE DERIVA- TIVES Curt Schuster, Karl Maier, Robert Gehm, and Julius Eisele, Ludwigshafen (Rhine), and Wilhelm Frederkiel, Frankenthal, Germany, assignors to Badische Anilin- & Soda-Fahrilr Aktiengesellschaft, Ludwigshafen am Rhine, Germany No Drawing. Application February 1, 1955, Serial No. 485,592

Claims priority, application Germany February 5, 1954 3 Claims. (Cl. 8-61) This invention relates to an improved process for improving the waste gas fastness of dyed cellulose derivatives.

it is already known that the shade of color and the clarity of dyed cellulose esters and ethers, especially in the form of fibres and fabrics, sometimes change in an undesirable manner in the air, and it has been found that this so-called acid-fading, which occurs in particular when using aminoanthraquinones as dyestuffs, is caused by nitrogen oxides present in the atmosphere. It is referred to as a bad waste gas fastness on the part of such dyeings.

We have now found that the waste gas fastness of dyed cellulose derivatives can be considerably improved by treating them before or after dyeing or in the dyebath itself with small amounts of colorless esters of hydroxyalkylamines. The said esters may also be spun into the fibres produced from the cellulose derivatives. Instead of the free amino esters, it is also possible to use their reaction products with formaldehyde and bisulfites.

Suitable hydroxyalkylamines of which the esters may be used for the process according to this invention are for example those having the general formula in which m, n and x are whole numbers greater than 1 and R and R are identical or different aliphatic, cycloaliphatic or araliphatic radicals; R and R may also be members of a common isocyclic or heterocyclic ring.

Examples of such hydroxyalkylamines are beta-.diethyL aminoethanol or -propanol, gamma-dibutylaminopropanol, N-beta-hydroxyethylpyrrolidine or -piperidine, N-beta-hydroxyethylimidazole, N-methy1-, N-ethy1-, N- cyclohexylor N-benzyl-di-(hydroxyethyD-amine or N.N- dihydroxyethylpiperazine.

For the process according to this invention there may be used for example the esters of the said hydroxyalkylamines with aromatic, araliphatic and cycloaliphatic carboxylic acids, such as benzoic acid, alkylbenzoic acids, phenylacetic acid, cyclohexyl and cyclohexenyl carboxylic acids, but the esters of aliphatic carboxylic acids, such as acetic, isobutyric or oleic acids are also suitable. Carbamic acid esters of the said hydroxyalkylamines, which are preferably prepared by reaction of the hydroxyalkylamines with organic isocyanates, are also suitable. Suitable isocyanates are for example phenyl isocyanate, hexamethylene di-isocyanate, toluylene di-isocyanate. Of quite general application are carbamic acid esters which have been obtained by reaction of monofunctional isocyanates with aminoalcohols containing one or more hydroxyl groups or by reaction of aminoalcohols containing one hydroxyl group with monofunctional or polyfunctional isocyanates.

The following examples will further illustate this invention but the invention is not restricted to these examples.

Example 1 1000 grams of an acetate rayon fabric are moved for about an hour at C. in 20 litres of an aqueous bath containing 10 grams of finely divided 1.4.5.8-tetra-aminoanthraquinone and 40 grams of dispersed N.N'-bis-(2- benzoyloxy-ethyl) -piperazine CHPCHQ The fabric finished oil in the usual manner is dyed midblue shades of very good waste gas fastness.

(CeHs-C O O-CHz-CHz-N Example 2 4 100 gramof an acetate rayon skein are dyed for an hour at C. in 2 litres of an aqueous bath with 0.5 gram of finely divided 1-amino-2-methoxy-4-hydroxyanthraquinone. After rinsing, the tdyed skein is treated for 20 minutes at 75 C. with a bath ratio of 1:20 with an aqueous bath containing 2 grams of N-benzoyloxyethylirnidazole in emulsified form. The rose dyeing obtained has very good waste gas fastness.

Example 3 grams of an acetate rayon fabric are moved for 45 minutes at 75 C. to 80 C. in 4 litres of water which contain 3 grams of finely divided 1.4-diaminoantbraquinone and 6 grams of bis-benzoic acid ester of N- butyldiethanolamine (n-C4H9N(CH2CH2OOCC6H5)2 in emulsified form. A violet dyeing is obtained having a good waste gas fastness.

A similar action is obtained by using the bis-phenylacetic acid ester of N-methyldiethanolamine (HsC-N(CH2CH2OOC-CH2C6H5)2 instead of or in addition to the abovementioned ester.

Example 4 1000 grams of an acetate rayon fabric is moved for an hour at 75 C. in 40 litres of water which contain 30 grams of finely divided 1.4-di-(methylamino)-anthraquinone and 60 grams of dispersed bis-hexahydrobenzoic acid ester of N.N-di(beta-hydroxyethyl)-piperazine. A deep blue dyeing of very good waste gas fastness is obtained.

Example 5 3 acid amide in 1000 litres of water. The clear blue dyeings thus obtained have very good waste gas fastness.

Example 6 100 grams of an acetate rayon fabric are dyed for an hour at 80 C. in 3 litres of water which contain 1 gram of finely divided l.4-dimethylaminoanthraquinone and 1 gram of the carbamic acid ester in finely divided form prepared from 2 mols of phenylisocyanate and 1 mol of methyldiethanolamine. T he dyed fabric is then finished off as usual. Brilliant blue dyeings with very good waste gas fastness are obtained.

Example 7 100 grams of an acetate rayon skein are dyed for 45 minutes at 75 C. in 2 litres of water which contain 0.2 gram of finely divided 1.4-diaminoanthraquinone and 0.8 gram of the carbamic acid ester in finely divided form prepared from 2 mols of phenylisocyanate and 1 mol of N.N'-di-(hydroxyethyD-piperazine. Delicate violet dyeings with very good waste gas fastness are obtained.

Example 8 100 grams of an acetate rayon fabric are dyed for 45 minutes at 80 C. in 4 litres of water which contain 2 grams of finely divided 1.4.S-triaminoanthraquinone. The dyeing is rinsed and then treated for 30 minutes at 75 C. in a further bath consisting of 4 litres of water and 1 gram of the carbamic acid ester prepared from 3 mols of phenyl isocyanate and 1 mol of triethanolamine. Deep blue dyeings with very good waste gas fastness are obtained.

Example 9 An acetone solution of 10 kilograms of the carbamic acid ester prepared from 1 mol of phenylisocyanate and 1 mol of N-dimethylisopropanolamine is aded to a spinning solution consisting of 1000 kilograms of acetyl cellulose dissolved in acetone, and the mixture is spun into threads in the conventional manner.

100 kilograms of these acetate rayon threads are dyed in 2000 litres of water which contain 1 kilogram of finely divided l.4 diaminoanthraquinone for an hour at 85 C. Pale violet dyeings with very good waste gas fastness are obtained.

Example 10 100 grams of an acetate rayon fabric are dyed for 45 minutes at 85 C. in 3 litres of water which contain 1 gram of finely divided 1-amino-2-methoxy-4 hydroxyanthraquinone and 1.5 grams of the carbamic acid ester prepared from 1 mol of phenyl isocyanate and 1 mol of N-dipropylethanolamine, in finely [divided form. Rose dyeings with very good waste gas fastness are obtained.

Example 11 The procedure of Example 10 is followed but using instead of the phenyl carbamic acid ester of N-dipropylethanolamine, the carbamic acid ester prepared from 1 mol of phenyl isocyanate and 1 mol of N-viny1-2-methylolimidazole. Rose dyeings with very good waste gas fastness are similarly obtained.

Example 12 100 grams of an acetate rayon fabric are dyed for an hour at 75 C. to 85 C. in 4 litres of water which contain 0.5 gram of finely divided 1-amino-4-methylaminoanthraquinone-Z-carboxylic acid amide and 2 grams of the carbamic acid ester prepared from 1 mol of hexamethylene di-isocyanate and 2 mols of N-dimethyl-isopropanolamine. Pale blue dyeings with very good waste gas fastness are obtained.

Example 13 If, instead of the carbamic acid ester of Example 12, there is used the same amount of the carbamic acid ester prepared from 1 mol of hexamethylene di-isocyanate and 4 2 mols of N-dipropylethanolamine, pale blue dyeings of very good waste gas fastness are similarly obtained.

Example 14 100 grams of an acetate rayon skein are dyed for an hour at C. in 2 litres of water which contain 1.5 grams of finely divided 1.4.5.8-tctraminoanthraquinone and 1 gram of the carbamic acid ester prepared from 2 mols of phenyl isocyanate and 1 mol of N-butyl-diethanolamine, in finely diivded form. Blue dyeings with very good waste gas fastness are obtained.

Example 15 1f 1.5 grams of the carbamic acid ester prepared from 1 mol of phenyl isocyanate and 1 mol of N-hydroxyethylpyrrolidine be used instead of the product specified in Example 14, dyeings with very good waste gas fastness are similarly obtained.

Example 16 An acetone solution of 1 kilogram of the product specified in Example 15 is added to a spinning solution consisting of kilograms of acetyl cellulose dissolved in acetone and the mixture is spun to threads in the usual fashion.

100 grams of this acetate rayon thread are dyed in a bath which consists of 2 litres of water and 0.5 gram of finely divided l.4-dirnethylaminoanthraquinone for 45 minutes at 80 C. Pale blue dyeings with very good waste gas fastness are obtained.

Example 17 If 1 kilogram of the carbamic acid ester prepared from 1 mol of toluylene di-isocyanate and 2 mols of N-hydroxyethylpyrrolidine be used instead of 1 kilogram of the product specified in Example 15, dyeings of very good waste gas fastness similarly result upon dyeing.

Example 18 100 grams of an acetate rayon fabric are treated for an hour at 80 C. in 3 litres of water which contain 2 grams of finely divided 1.4-diamino-S-nitroanthraquinone and 2 grams of the carbamic acid ester in finely divided form prepared from 1 mol of alpha-diethylamino-N-hydroxyethylpyrrolidine and 1 mol of phenyl isocyanate. Violet dyeings with very good waste gas fastness result.

Example 19 100 grams of an acetate rayon fabric are dyed for an hour at 75 C. to 80 C. in 2 litres of water which contain 1.5 grams of finely divided 1-amino-4-methylaminoanthraquinone-2-carboxylic acid amide and 1 gram of the carbarnic acid ester in finely divided form prepared from 1 mol of phenyl isocyanate and 1 mol of 1.3-bis-diethy1- aminoisopropanol. Mid-blue dyeings with very good waste gas fastness are obtained.

What we claim is:

1. A process for improving the fastness of colorations of water-insoluble dyestufifs on cellulose acetate textile material to acid fading which comprises incorporating in such textile material a carbamic acid ester of the general formula wherein R stands for a saturated aliphatic radical.

2. A process for improving the fastness of colorations of water-insoluble dyestuffs on cellulose acetate textile material to acid fading which comprises incorporating in such textile material the carbamic acid ester of the formula 3. A process for improving the fastness of colorations of water-insoluble dyestufis on cellulose acetate textile 6 material to acid fading which comprises incorporating in 2,094,809 Olpin Oct. 5, 1937 such textile material the carbamic acid ester of the 2,539,212 Strobel Jan. 23, 1951 formula 2,706,142 Von Glahn Apr. 12, 1955 n-C4H9N(CH2CH2-OCO-NH-CaH5)2 5 OTHER REFERENCES Br. Rayon and Silk Journal for December 1951, pp.

References Cited in the file of this patent 63 64 UNITED STATES PATENTS 2,083,122 Olpin June 8, 1937 

1. A PROCESS FOR IMPROVING THE FASTNESS OF COLORATIONS OF WATER-INSOLUBLE DYESTUFFS ON CELLULOSE ACETATE TEXTILE MATERIAL TO ACID FADING WHICH COMPRISES INCORPORATING IN SUCH TEXTILE MATERIAL A CARBAMIC ACID ESTER OF THE GENERAL FORMULA 